U.S. patent number 10,696,928 [Application Number 16/352,913] was granted by the patent office on 2020-06-30 for detergent compositions contained in a water-soluble film containing a leuco colorant.
This patent grant is currently assigned to The Procter & Gamble Company. The grantee listed for this patent is The Procter & Gamble Company. Invention is credited to Daniel Dale Ditullio, Gregory Scot Miracle.
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United States Patent |
10,696,928 |
Miracle , et al. |
June 30, 2020 |
Detergent compositions contained in a water-soluble film containing
a leuco colorant
Abstract
Detergent compositions comprising a water-soluble film and a
leuco colorant. At least about 10% of the leuco colorant is
incorporated into the water-soluble film. Methods of making such
detergent compositions. A detergent composition including (a) at
least one laundry care ingredient and (b) a leuco composition. The
leuco composition has a first color state and a second color state
and the mole ratio of second color state to first color state is
from 2:98 to 5:95. Also disclosed are methods of determining the
approximate functional age of a detergent composition comprising
the steps of (a) providing a detergent composition that includes at
least one laundry care ingredient and a leuco composition, (b)
providing a functional age scale that includes a plurality of
distinct colors that correspond to a unique functional age and (c)
comparing the color of the detergent composition with the
functional age scale.
Inventors: |
Miracle; Gregory Scot (Liberty
Township, OH), Ditullio; Daniel Dale (Hamilton, OH) |
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
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Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
65952223 |
Appl.
No.: |
16/352,913 |
Filed: |
March 14, 2019 |
Prior Publication Data
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|
Document
Identifier |
Publication Date |
|
US 20190292496 A1 |
Sep 26, 2019 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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62645821 |
Mar 21, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D
3/42 (20130101); C11D 3/40 (20130101); C11D
17/043 (20130101); C11D 17/045 (20130101); C11D
17/042 (20130101); C09B 11/12 (20130101); C11D
3/0084 (20130101) |
Current International
Class: |
C11D
3/40 (20060101); C11D 3/42 (20060101); C11D
17/04 (20060101); C09B 11/12 (20060101); C11D
3/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
US. Appl. No. 16/352,917, filed Mar. 14, 2019, Miracle, et al.
cited by applicant.
|
Primary Examiner: Boyer; Charles I
Attorney, Agent or Firm: Dipre; John T.
Claims
What is claimed is:
1. A detergent composition comprising: a) a first composition; b) a
water-soluble film; and c) a leuco colorant wherein said first
composition is selected from the group consisting of a liquid
detergent, a granular detergent, or a tablet detergent, and wherein
at least about 30% of said leuco colorant is incorporated into said
water-soluble film.
2. A detergent composition according to claim 1, wherein the leuco
colorant is selected from the group consisting of a diarylmethane
leuco, a triarylmethane leuco, an oxazine leuco, a thiazine leuco,
a hydroquinone leuco, an arylaminophenol leuco and mixtures
thereof.
3. A detergent composition according to claim 1, wherein the leuco
colorant is selected from one or more compounds selected from the
group consisting of: ##STR00009## and (f) mixtures thereof; wherein
the ratio of Formula I-V to its oxidized form is at least 1:3;
wherein each individual R.sub.o, R.sub.m and R.sub.p group on each
of rings A, B and C is independently selected from the group
consisting of hydrogen, deuterium and R.sup.5; wherein each R.sup.5
is independently selected from the group consisting of halogens,
nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl,
substituted alkaryl, --C(O)R.sup.1, --C(O)OR.sup.1, --C(O)O.sup.-,
--C(O)NR.sup.1R.sup.2, --OC(O)R.sup.1, --OC(O)OR.sup.1,
--OC(O)NR.sup.1R.sup.2, --S(O).sub.2R.sup.1, --S(O).sub.2OR.sup.1,
--S(O).sub.2O.sup.-, --S(O).sub.2NR.sup.1R.sup.2,
--NR.sup.1C(O)R.sup.2, --NR.sup.1C(O)OR.sup.2,
--NR.sup.1C(O)SR.sup.2, --NR.sup.1C(O)NR.sup.2R.sup.3, --OR.sup.1,
--NR.sup.1R.sup.2, --P(O).sub.2R.sup.1, --P(O)(OR.sup.1).sub.2,
--P(O)(OR.sup.1)O.sup.-, and --P(O)(O.sup.-).sub.2; wherein at
least one of the R.sub.o and R.sub.m groups on at least one of the
three rings A, B or C is hydrogen; each R.sub.p is independently
selected from hydrogen, --OR.sup.1 and --NR.sup.1R.sup.2; wherein G
is independently selected from the group consisting of hydrogen,
deuterium, C.sub.1-C.sub.16 alkoxide, phenoxide, bisphenoxide,
nitrite, nitrile, alkyl amine, imidazole, arylamine, polyalkylene
oxide, halides, alkylsulfide, aryl sulfide, and phosphine oxide;
wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected
from the group consisting of hydrogen, alkyl, substituted alkyl,
aryl, substituted aryl, alkaryl, substituted alkaryl, and R.sup.4;
R.sup.4 is a organic group composed of one or more organic monomers
with said monomer molecular weights ranging from 28 to 500; wherein
e and f are independently integers from 0 to 4; wherein each
R.sup.20 and R.sup.21 is independently selected from the group
consisting of a halogen, a nitro group, alkyl groups, substituted
alkyl groups, --NC(O)OR.sup.1, --NC(O)SR.sup.1, --OR.sup.1, and
--NR.sup.1R.sup.2; wherein each R.sup.25 is independently selected
from the group consisting of a monosaccharide moiety, a
disaccharide moiety, an oligosaccharide moiety, a polysaccharide
moiety, --C(O)R.sup.1, --C(O)OR.sup.1, --C(O)NR.sup.1R.sup.2;
wherein each R.sup.22 and R.sup.23 is independently selected from
the group consisting of hydrogen, an alkyl group, and substituted
alkyl groups; wherein R.sup.30 is positioned ortho or para to the
bridging amine moiety and is selected from the group consisting of
--OR.sup.38 and --NR.sup.36R.sup.37, wherein each R.sup.36 and
R.sup.37 is independently selected from the group consisting of
hydrogen, an alkyl group, a substituted alkyl group, an aryl group,
a substituted aryl group, an acyl group, R.sup.4, --C(O)OR.sup.1,
--C(O)R.sup.1, and --C(O)NR.sup.1R.sup.2; wherein R.sup.38 is
selected from the group consisting of hydrogen, an acyl group,
--C(O)OR.sup.1, --C(O)R.sup.1, and --C(O)NR.sup.1R.sup.2; wherein g
and h are independently integers from 0 to 4; wherein each R.sup.31
and R.sup.32 is independently selected from the group consisting of
an alkyl group, a substituted alkyl group, an aryl group, a
substituted aryl group, an alkaryl, substituted alkaryl,
--C(O)R.sup.1, --C(O)OR.sup.1, --C(O)O.sup.-,
--C(O)NR.sup.1R.sup.2, --OC(O)R.sup.1, --OC(O)OR.sup.1,
--OC(O)NR.sup.1R.sup.2, --S(O).sub.2R.sup.1, --S(O).sub.2OR.sup.1,
--S(O).sub.2O.sup.-, --S(O).sub.2NR.sup.1R.sup.2,
--NR.sup.1C(O)R.sup.2, --NR.sup.1C(O)OR.sup.2,
--NR.sup.1C(O)SR.sup.2, --NR.sup.1C(O)NR.sup.2R.sup.3, --OR.sup.1,
--NR.sup.1R.sup.2, --P(O).sub.2R.sup.1, --P(O)(OR.sup.1).sub.2,
--P(O)(OR.sup.1)O.sup.-, and --P(O)(O.sup.-).sub.2; wherein
--NR.sup.34R.sup.35 is positioned ortho or para to the bridging
amine moiety and R.sup.34 and R.sup.35 are independently selected
from the group consisting of hydrogen, an alkyl, a substituted
alkyl, an aryl, a substituted aryl, an alkaryl, a substituted
alkaryl, and R.sup.4; wherein R.sup.33 is independently selected
from the group consisting of hydrogen, --S(O).sub.2R.sup.1,
--C(O)N(H)R.sup.1; --C(O)OR.sup.1; and --C(O)R.sup.1; wherein when
g is 2 to 4, any two adjacent R.sup.31 groups may combine to form a
fused ring of five or more members wherein no more than two of the
atoms in the fused ring may be nitrogen atoms; wherein X.sup.40 is
selected from the group consisting of an oxygen atom, a sulfur
atom, and NR.sup.45; wherein R.sup.45 is independently selected
from the group consisting of hydrogen, deuterium, an alkyl, a
substituted alkyl, an aryl, a substituted aryl, an alkaryl, a
substituted alkaryl, --S(O).sub.2OH, --S(O).sub.2O.sup.-,
--C(O)OR.sup.1, --C(O)R.sup.1, and --C(O)NR.sup.1R.sup.2; wherein
R.sup.40 and R.sup.41 are independently selected from the group
consisting of --OR.sup.1 and --NR.sup.1R.sup.2; wherein j and k are
independently integers from 0 to 3; wherein R.sup.42 and R.sup.43
are independently selected from the group consisting of an alkyl, a
substituted alkyl, an aryl, a substituted aryl, an alkaryl, a
substituted alkaryl, --S(O).sub.2R.sup.1, --C(O)NR.sup.1R.sup.2,
--NC(O)OR.sup.1, --NC(O)SR.sup.1, --C(O)OR.sup.1, --C(O)R.sup.1,
--OR.sup.1, --NR.sup.1R.sup.2; wherein R.sup.44 is --C(O)R.sup.1,
--C(O)NR.sup.1R.sup.2, and --C(O)OR.sup.1; wherein any charge
present in any of the compounds is balanced with a suitable
independently selected internal or external counterion.
4. A detergent composition according to claim 3, wherein the leuco
colorant conforms to the structure of Formula VI, ##STR00010##
wherein each R.sup.4 is independently selected from the group
consisting of H, Methyl, Ethyl,
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H, and mixtures
thereof, wherein each index a is independently an integer from
1-100 and each index b is independently an integer from 0-50, and
wherein the sum of all the independently selected a integers in all
R.sup.4 groups is no more than 200, and the sum of all the
independently selected b integers in all R.sup.4 groups is no more
than 100.
5. A detergent composition according to claim 4, wherein the leuco
colorant conforms to the structure of Formula VII ##STR00011##
wherein each index c is independently 0, 1 or 2; each R.sup.4 is
independently selected from the group consisting of H, Me, Et,
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H, and mixtures
thereof, wherein each index a is independently an integer from
1-50; each index b is independently an integer from 0-25 and
wherein the sum of all the independently selected a integers in the
leuco colorant is no more than 100, and the sum of all the
independently selected b integers in the leuco colorant is no more
than 50.
6. A detergent composition according to claim 5, wherein the leuco
colorant conforms to the structure of Formula VIII ##STR00012##
wherein R.sup.8 is H or CH.sub.3 and each index b is independently
on average about 1 to 2.
7. A detergent composition according to claim 1, wherein at least
about 50% of the leuco colorant is incorporated into the
water-soluble film.
8. A detergent composition according to claim 1, wherein
substantially all of the leuco colorant is incorporated into the
water-soluble film.
9. A detergent composition according to claim 1, wherein the
detergent composition is in the form of a unit dose article.
10. A detergent composition according to claim 9, wherein the unit
dose article comprises a first film and a second film.
11. A detergent composition according to claim 10, wherein the
leuco colorant is incorporated into the first film.
12. A detergent composition according to claim 10, wherein the
leuco colorant is incorporated into both the first film and the
second film.
13. A detergent composition according to claim 10, wherein
substantially all of the leuco colorant is incorporated into the
first film.
14. A detergent composition according to claim 9, wherein the unit
dose article comprises a first film, a second film and a common
wall.
15. A detergent composition according to claim 14, wherein
substantially all of the leuco colorant is incorporated into the
common wall.
16. A detergent composition according to claim 1, wherein said
first composition comprises an adjunct selected from the group
consisting of surfactants, builders, chelating agents, dye transfer
inhibiting agents, dispersants, enzymes, enzyme stabilizers,
catalytic materials, bleach activators, polymeric dispersing
agents, clay soil removal agents, anti-redeposition agents,
brighteners, suds suppressors, dyes, perfume, perfume delivery
systems, structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids, pigments and mixtures thereof.
17. A detergent composition according to claim 1, further
comprising an antioxidant incorporated into at least a portion of
the water-soluble film, wherein the antioxidant is selected from
the group consisting of hindered phenols, diarylamines, and
mixtures thereof.
18. A method of determining the approximate functional age of a
detergent composition comprising the steps of: a) providing a
detergent composition according to present claim 1; b) providing a
functional age scale comprising a plurality of distinct colors
wherein each distinct color corresponds to a unique functional age;
and c) comparing the color of the detergent composition with the
functional age scale.
19. The method of determining the approximate functional age of a
detergent composition of claim 18, further comprising providing a
package and wherein the functional age scale is provided on the
package.
20. A detergent composition according to claim 1, wherein the leuco
colorant has a first color state and a second color state and the
mole ratio of second color state to first color state is from 2:98
to 25:75.
Description
FIELD OF THE INVENTION
The present disclosure relates in part to a detergent composition
comprising a water-soluble or water-dispersible film and a leuco
colorant. These types of colorants are provided in a stable,
substantially colorless state and then may be transformed to an
intense colored state upon exposure to certain physical or chemical
changes such as, for example, exposure to oxygen, ion addition,
exposure to light, and the like. This application further relates
to methods for determining the approximate functional age of a
detergent composition comprising a leuco composition. The invention
also relates to a process for making such a detergent
composition.
BACKGROUND OF THE INVENTION
Detergents today are available in a wide variety of forms such as
powders, granules, liquids and gels. Unit dose and concentrated (or
compact) detergent forms are becoming increasingly popular due to
the convenience they offer the consumer on lower weight and, in the
case of unit dose, simplified dosing. The highly concentrated
nature of these forms offers further sustainability advantages,
such as reduced shipping costs and environmental impact (e.g.
carbon footprint).
As detergent compositions age, it is known that they may become
more yellow due to any of a number of causes, including, for
example, exposure to light, heat, air permeating through the
package, natural degradation of the compositions components, or
reactions involving formulated components. Further, as many laundry
compositions age, their efficacy tends to decline as certain
components may degrade with age and lose potency. Consumers
accustomed to expiration dates on items understand that
formulations have some limited time in which they will function as
expected, after which they expect some decrease in the efficacy of
the product. However, few if any products provide the consumer a
means by which they can assess where a product in their possession
is in relation to its expected useful lifespan, even when a date of
production is on the package. This date of manufacture cannot
provide any information regarding the impact of the conditions to
which the product has been exposed between the date of manufacture
and the point of purchase. The date of manufacture indicates only
the maximum possible freshness and/or functioning of the product at
any point in time, but adverse storage conditions lead to
deterioration that decreases efficacy of certain ingredients (such
as enzymes) and there is no means by which a consumer may estimate
the functional age of the formulation.
It is also known that as textile substrates age, their color tends
to fade or yellow due to exposure to light, air, soil, and natural
degradation of the fibers that comprise the substrates. As such, to
visually enhance these textile substrates and counteract the fading
and yellowing the use of polymeric colorants for coloring consumer
products has become well known in the prior art. For example, it is
well known to use whitening agents, either optical brighteners or
bluing agents, in textile applications. However, due to the blue or
violet hue of traditional bluing agents, formulators have been
constrained to using traditional bluing agents in dark blue
detergent compositions that show little if any color change over
time.
Leuco dyes are also known in the prior art to exhibit a change from
a colorless or slightly colored state to a colored state upon
exposure to specific chemical or physical triggers. The change in
coloration that occurs is typically visually perceptible to the
human eye. Most organic compounds have some absorbance in the
visible light region (400-750 nm), and thus more or less have some
color. As referred to herein, a dye is considered as a "leuco dye"
if it did not render a significant color at its application
concentration and conditions, but renders a significant color in
its triggered form. The color change upon triggering stems from the
change of the molar attenuation coefficient (also known as molar
extinction coefficient, molar absorption coefficient, and/or molar
absorptivity in some literatures) of the leuco dye molecule in the
400-750 nm range, preferably in the 500-650 nm range, and most
preferably in the 530-620 nm range. The increase of the molar
attenuation coefficient of a leuco dye before and after the
triggering should be bigger than 50%, more preferably bigger than
200%, and most preferably bigger than 500%.
As such, there remains a need for a consumer to assess the
estimated functional age of a unit dose composition and, thereby,
the composition's estimated efficacy.
It has now surprisingly been found that the presently claimed leuco
colorants incorporated into the film of a unit dose composition
develop their color over time in response to environmental factors
such as the temperatures to which they have been exposed, thereby
providing the consumer with an estimated functional age of the
compositions. Additionally, where the leuco colorants develop blue
color, they can be used to counteract the natural yellowing of aged
detergent compositions, and will typically be designed to deposit
on fabric through the wash, either in their leuco form, or in their
oxidized form to provide a whiteness enhancement to aged
fabrics.
SUMMARY OF THE INVENTION
The present disclosure relates to a detergent composition
comprising a first composition, a water-soluble film, and a leuco
colorant. The first composition is selected from the group
consisting of a liquid detergent, a granular detergent, or a tablet
detergent, and at least about 10% of the leuco colorant is
incorporated into the water-soluble film.
In another aspect, the present invention relates to a method of
determining the approximate functional age of a detergent
composition comprising the steps of (a) providing a detergent
composition comprising (i) a water-soluble film, (ii) at least one
laundry care ingredient, and (iii) a leuco composition; (b)
providing a functional age scale comprising a plurality of distinct
colors wherein each distinct color corresponds to a unique
functional age; and (c) comparing the color of the detergent
composition with the functional age scale.
The present disclosure also relates to a method of making a
detergent composition comprising a first composition, a
water-soluble film and a leuco colorant. The method comprises the
steps of incorporating the leuco colorant into the film, optionally
incorporating an antioxidant into the film, and encapsulating the
first composition in the water-soluble film.
The present disclosure also relates to a detergent composition
comprising (a) a water-soluble film, (b) at least one laundry care
ingredient and (c) a leuco colorant. The leuco colorant has a first
color state and a second color state and the mole ratio of second
color state to first color state is from 2:98 to 25:75, preferably
2:98 to 15:85, or to 10:90, or even to 5:95.
The present disclosure also relates to a unit dose detergent
composition comprising at least one compartment, a water-soluble
film, and a leuco colorant. At least about 10% of the leuco
colorant is incorporated into the water-soluble film.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a unit dose article according to the
present invention;
FIG. 2 is a side view of another embodiment of unit dose article
according to the present invention;
FIG. 3 is a side view of another embodiment of unit dose article
according to the present invention;
FIG. 4 is a side view of another embodiment of unit dose article
according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present disclosure relates to detergent compositions that
comprise a water-soluble film and a leuco colorant.
Definitions
Features and benefits of the various embodiments of the present
invention will become apparent from the following description,
which includes examples of specific embodiments intended to give a
broad representation of the invention. Various modifications will
be apparent to those skilled in the art from this description and
from practice of the invention. The scope is not intended to be
limited to the particular forms disclosed and the invention covers
all modifications, equivalents, and alternatives falling within the
spirit and scope of the invention as defined by the claims.
As used herein, the articles including "the," "a" and "an" when
used in a claim or in the specification, are understood to mean one
or more of what is claimed or described.
As used herein, the terms "include," "includes" and "including" are
meant to be non-limiting. The phases "comprising" or "comprises"
are intended to include the more limiting phrases "consisting
essentially of" and "consisting of." Therefore, a composition that
comprises a component may consist essentially of that component, or
consist of that component.
As used herein, the terms "substantially free of" or "substantially
free from" mean that the indicated material is at the very minimum
not deliberately added to the composition to form part of it, or,
preferably, is not present at analytically detectable levels. It is
meant to include compositions whereby the indicated material is
present only as an impurity in one of the other materials
deliberately included.
As used herein, the term "soiled material" is used non-specifically
and may refer to any type of flexible material consisting of a
network of natural or artificial fibers, including natural,
artificial, and synthetic fibers, such as, but not limited to,
cotton, linen, wool, polyester, nylon, silk, acrylic, and the like,
as well as various blends and combinations. Soiled material may
further refer to any type of hard surface, including natural,
artificial, or synthetic surfaces, such as, but not limited to,
tile, granite, grout, glass, composite, vinyl, hardwood, metal,
cooking surfaces, plastic, and the like, as well as blends and
combinations.
As used herein, the term "alkoxy" is intended to include
C.sub.1-C.sub.8 alkoxy and alkoxy derivatives of polyols having
repeating units such as butylene oxide, glycidol oxide, ethylene
oxide or propylene oxide.
As used herein, the interchangeable terms "alkyleneoxy" and
"oxyalkylene," and the interchangeable terms "polyalkyleneoxy" and
"polyoxyalkylene," generally refer to molecular structures
containing one or more than one, respectively, of the following
repeating units: --C.sub.2H.sub.4O.sup.-, --C.sub.3H.sub.6O.sup.-,
--C.sub.4H.sub.8O--, and any combinations thereof. Non-limiting
structures corresponding to these groups include
--CH.sub.2CH.sub.2O--, --CH.sub.2CH.sub.2CH.sub.2O.sup.-,
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2O--, --CH.sub.2CH(CH.sub.3)O--,
and --CH.sub.2CH(CH.sub.2CH.sub.3)O--, for example. Furthermore,
the polyoxyalkylene constituent may be selected from the group
consisting of one or more monomers selected from a C.sub.2-20
alkyleneoxy group, a glycidyl group, or mixtures thereof.
The terms "ethylene oxide," "propylene oxide" and "butylene oxide"
may be shown herein by their typical designation of "EO," "PO" and
"BO," respectively.
As used herein, the terms "alkyl" and "alkyl capped" are intended
to mean any univalent group formed by removing a hydrogen atom from
a substituted or unsubstituted hydrocarbon. Non-limiting examples
include hydrocarbyl moieties which are branched or unbranched,
substituted or unsubstituted including C.sub.1-C.sub.18 alkyl
groups, and in one aspect, C.sub.1-C.sub.6 alkyl groups. As used
herein, unless otherwise specified, the term "aryl" is intended to
include C.sub.3-C.sub.12 aryl groups. The term "aryl" refers to
both carbocyclic and heterocyclic aryl groups. As used herein, the
term "alkaryl" refers to any alkyl-substituted aryl substituents
and aryl-substituted alkyl substituents. More specifically, the
term is intended to refer to C.sub.7-16 alkyl-substituted aryl
substituents and C.sub.7-16 aryl substituted alkyl substituents
which may or may not comprise additional substituents. As used
herein, the term "laundry care composition" includes, unless
otherwise indicated, granular, powder, liquid, gel, paste, unit
dose, bar form and/or flake type washing agents and/or fabric
treatment compositions, including but not limited to products for
laundering fabrics, fabric softening compositions, fabric enhancing
compositions, fabric freshening compositions, and other products
for the care and maintenance of fabrics, and combinations thereof.
Such compositions may be pre-treatment compositions for use prior
to a washing step or may be rinse added compositions, as well as
cleaning auxiliaries, such as bleach additives and/or "stain-stick"
or pre-treat compositions or substrate-laden products such as dryer
added sheets. As used herein, the term "leuco" (as used in
reference to, for example, a compound, moiety, radical, dye,
monomer, fragment, or polymer) refers to an entity (e.g., organic
compound or portion thereof) that, upon exposure to specific
chemical or physical triggers, undergoes one or more chemical
and/or physical changes that results in a shift from a first color
state (e.g., uncolored or substantially colorless) to a second more
highly colored state. Suitable chemical or physical triggers
include, but are not limited to, oxidation, pH change, temperature
change, and changes in electromagnetic radiation (e.g., light)
exposure. Suitable chemical or physical changes that occur in the
leuco entity include, but are not limited to, oxidation and
non-oxidative changes, such as intramolecular cyclization. Thus, in
one aspect, a suitable leuco entity can be a reversibly reduced
form of a chromophore. In one aspect, the leuco moiety preferably
comprises at least a first and a second .pi.-system capable of
being converted into a third combined conjugated .pi.-system
incorporating said first and second .pi.-systems upon exposure to
one or more of the chemical and/or physical triggers described
above. As used herein, the terms "leuco composition" or "leuco
colorant composition" refers to a composition comprising at least
two leuco compounds having independently selected structures as
described in further detail herein. As used herein "average
molecular weight" of the leuco colorant is reported as a weight
average molecular weight, as determined by its molecular weight
distribution: as a consequence of their manufacturing process, the
leuco colorants disclosed herein may contain a distribution of
repeating units in their polymeric moiety. As used herein, the
terms "maximum extinction coefficient" and "maximum molar
extinction coefficient" are intended to describe the molar
extinction coefficient at the wavelength of maximum absorption
(also referred to herein as the maximum wavelength), in the range
of 400 nanometers to 750 nanometers. As used herein, the term
"converting agent" refers to any oxidizing agent as known in the
art other than molecular oxygen in any of its known forms (singlet
and triplet states). As used herein, the term "triggering agent"
refers to a reactant suitable for converting the leuco composition
from a colorless or substantially colorless state to a colored
state. As used herein, the term "whitening agent" refers to a dye
or a leuco colorant that may form a dye once triggered that when on
white cotton provides a hue to the cloth with a relative hue angle
of 210 to 345, or even a relative hue angle of 240 to 320, or even
a relative hue angle of 250 to 300 (e.g., 250 to 290). As used
herein, "cellulosic substrates" are intended to include any
substrate which comprises at least a majority by weight of
cellulose. Cellulose may be found in wood, cotton, linen, jute, and
hemp. Cellulosic substrates may be in the form of powders, fibers,
pulp and articles formed from powders, fibers and pulp. Cellulosic
fibers, include, without limitation, cotton, rayon (regenerated
cellulose), acetate (cellulose acetate), triacetate (cellulose
triacetate), and mixtures thereof. Articles formed from cellulosic
fibers include textile articles such as fabrics. Articles formed
from pulp include paper. As used herein, articles such as "a" and
"an" when used in a claim, are understood to mean one or more of
what is claimed or described. As used herein, the terms "include/s"
and "including" are meant to be non-limiting. As used herein, the
term "solid" includes granular, powder, bar and tablet product
forms. As used herein, the term "fluid" includes liquid, gel, paste
and gas product forms. Unless otherwise noted, all component or
composition levels are in reference to the active portion of that
component or composition, and are exclusive of impurities, for
example, residual solvents or by-products, which may be present in
commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight unless
otherwise indicated. All percentages and ratios are calculated
based on the total composition unless otherwise indicated.
In one aspect, the molar extinction coefficient of said second
colored state at the maximum absorbance in the wavelength in the
range 200 to 1,000 nm (more preferably 400 to 750 nm) is preferably
at least five times, more preferably 10 times, even more preferably
25 times, most preferably at least 50 times the molar extinction
coefficient of said first color state at the wavelength of the
maximum absorbance of the second colored state. Preferably, the
molar extinction coefficient of said second colored state at the
maximum absorbance in the wavelength in the range 200 to 1,000 nm
(more preferably 400 to 750 nm) is at least five times, preferably
10 times, even more preferably 25 times, most preferably at least
50 times the maximum molar extinction coefficient of said first
color state in the corresponding wavelength range. An ordinarily
skilled artisan will realize that these ratios may be much higher.
For example, the first color state may have a maximum molar
extinction coefficient in the wavelength range from 400 to 750 nm
of as little as 10 M.sup.-1 cm.sup.-1, and the second colored state
may have a maximum molar extinction coefficient in the wavelength
range from 400 to 750 nm of as much as 80,000 M.sup.-1 cm.sup.-1 or
more, in which case the ratio of the extinction coefficients would
be 8,000:1 or more.
In one aspect, the maximum molar extinction coefficient of said
first color state at a wavelength in the range 400 to 750 nm is
less than 1000 M.sup.-1 cm.sup.-1, and the maximum molar extinction
coefficient of said second colored state at a wavelength in the
range 400 to 750 nm is more than 5,000 M.sup.-1 cm.sup.-1,
preferably more than 10,000, 25,000, 50,000 or even 100,000
M.sup.-1 cm.sup.-1. A skilled artisan will recognize and appreciate
that a polymer comprising more than one leuco moiety may have a
significantly higher maximum molar extinction coefficient in the
first color state (e.g., due to the additive effect of a
multiplicity of leuco moieties or the presence of one or more leuco
moieties converted to the second colored state). Detergent
Composition
As used herein, the phrase "detergent composition" includes
compositions and formulations designed for cleaning soiled
material. Such compositions include, but are not limited to,
laundry cleaning compositions and detergents, fabric softening
compositions, fabric enhancing compositions, fabric freshening
compositions, laundry prewash, laundry pretreat, laundry additives,
spray products, dry cleaning agent or composition, laundry rinse
additive, wash additive, post-rinse fabric treatment, ironing aid,
dish washing compositions, hard surface cleaning compositions, unit
dose formulation, delayed delivery formulation, detergent contained
on or in a porous substrate or nonwoven sheet, and other suitable
forms that may be apparent to one skilled in the art in view of the
teachings herein. Such compositions may be used as a pre-laundering
treatment, a post-laundering treatment, or may be added during the
rinse or wash cycle of the laundering operation. The detergent
compositions may have a form selected from liquid, powder, slurry,
single-phase or multi-phase unit dose articles, pouch, tablet, gel,
paste, bar, or flake.
In some aspects, the detergent composition comprises a first
composition where the first composition is selected from the group
consisting of a liquid detergent, a granular detergent, or a tablet
detergent. Preferably, when the first composition is a granular
detergent or a tablet detergent, the first composition is encased
in either a water-soluble film or a water-soluble coating.
Liquid detergent compositions and other forms of detergent
compositions that include a liquid component (such as
liquid-containing unit dose detergent compositions) may contain
water and other solvents as fillers or carriers. Low molecular
weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric
alcohols may be used in some examples for solubilizing surfactants,
and polyols such as those containing from 2 to about 6 carbon atoms
and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) may also be used.
Amine-containing solvents may also be used. Solvents particularly
useful in unit dose articles are described below.
The detergent compositions may contain from about 5% to about 90%,
and in some examples, from about 10% to about 50%, by weight of the
composition, of such carriers. For compact or super-compact heavy
duty liquid or other forms of detergent compositions, the use of
water may be lower than about 40% by weight of the composition, or
lower than about 20%, or lower than about 5%, or less than about 4%
free water, or less than about 3% free water, or less than about 2%
free water, or substantially free of free water (i.e.,
anhydrous).
The liquid detergent compositions may comprise water. However, when
the liquid composition will be in contact with water-soluble film,
for example in a unit dose article, it is typically desirable to
limit the amount of water so as to preserve the film's integrity
and to prevent a tacky feel to the pouches. Therefore, in some
embodiments, the liquid detergent composition comprises less than
about 50% water by weight of the liquid composition, or less than
about 40% water by weight of the liquid composition, or from about
1% to about 30%, or preferably from about 2% to about 20%, or from
about 5% to about 13%, water by weight of the liquid
composition.
For powder or bar detergent compositions, or forms that include a
solid or powder component (such as powder-containing unit dose
detergent composition), suitable fillers may include, but are not
limited to, sodium sulfate, sodium chloride, clay, or other inert
solid ingredients. Fillers may also include biomass or decolorized
biomass. Fillers in granular, bar, or other solid detergent
compositions may comprise less than about 80% by weight of the
detergent composition, and in some examples, less than about 50% by
weight of the detergent composition. Compact or supercompact powder
or solid detergent compositions may comprise less than about 40%
filler by weight of the detergent composition, or less than about
20%, or less than about 10%.
For either compacted or supercompacted liquid or powder detergent
compositions, or other forms, the level of liquid or solid filler
in the product may be reduced, such that either the same amount of
active chemistry is delivered to the wash liquor as compared to
noncompacted detergent compositions, or in some examples, the
detergent composition is more efficient such that less active
chemistry is delivered to the wash liquor as compared to
noncompacted compositions. For example, the wash liquor may be
formed by contacting the detergent composition to water in such an
amount so that the concentration of detergent composition in the
wash liquor is from above 0 g/l to 4 g/l. In some examples, the
concentration may be from about 1 g/l to about 3.5 g/l, or to about
3.0 g/l, or to about 2.5 g/l, or to about 2.0 g/l, or to about 1.5
g/l, or from about 0 g/l to about 1.0 g/l, or from about 0 g/l to
about 0.5 g/l. These dosages are not intended to be limiting, and
other dosages may be used that will be apparent to those of
ordinary skill in the art.
In some aspects, referring to the embodiments in FIGS. 1-4, the
detergent composition is in the form of a unit dose article 10. The
unit dose article 10 comprises at least one compartment, wherein
the compartment comprises a composition, for example a first
composition 20. A unit dose article 10 is intended to provide a
single, easy to use dose of the composition contained within the
article for a particular application. In some aspects, the
detergent composition is in unit dose form 10 and comprises
water-soluble film that encapsulates a liquid detergent.
The compartment should be understood as meaning a closed internal
space within the unit dose article, which holds the composition.
Preferably, the unit dose article comprises a water-soluble film.
The unit dose article is manufactured such that the water-soluble
film completely surrounds the composition and in doing so defines
the compartment in which the composition resides. The unit dose
article may comprise two films. A first film 40 may be shaped to
comprise an open compartment into which the composition is added. A
second film 50 is then laid over the first film 40 in such an
orientation as to close the opening of the compartment. The first
40 and second 50 films are then sealed together along a seal region
70. The seal region 70 may comprise a flange. The flange is
comprised of excess sealed film material that protrudes beyond the
edge of the unit dose article and provides increased surface area
for seal of the first 40 and second 50 films. The film is described
in more detail below. In some aspects, the unit dose article 10
comprises three, four, five or more films.
The unit dose article 10 may comprise more than one compartment,
even at least two compartments, or even at least three
compartments. In some aspects, the unit dose article 10 comprises
1, or 2, or 3, or 4, or 5 compartments. The compartments may be
arranged in superposed orientation, i.e., one positioned on top of
the other, as shown in FIG. 3, where they may share a common wall
60. In one aspect, at least one compartment is superposed on
another compartment. Alternatively, the compartments may be
positioned in a side-by-side orientation, i.e., one orientated next
to the other, as shown in FIG. 4. The compartments may even be
orientated in a `tire and rim` arrangement, i.e., a first
compartment is positioned next to a second compartment, but the
first compartment at least partially surrounds the second
compartment, but does not completely enclose the second
compartment. Alternatively, one compartment may be completely
enclosed within another compartment.
When the unit dose article comprises at least two compartments, one
of the compartments may be smaller than the other compartment. When
the unit dose article comprises at least three compartments, two of
the compartments may be smaller than the third compartment, and
preferably the smaller compartments are superposed on the larger
compartment. The smaller superposed compartments preferably are
orientated side-by-side.
When the unit dose article comprises at least two compartments,
each compartment may comprise identical compositions, or each
compartment may independently comprise a different composition. The
compartments may be sensorially different; for example, the
compartments may have different shapes, or they may be different
colors.
The encapsulated compositions may be any suitable composition. The
composition may be in the form of a solid, a liquid, a dispersion,
a gel, a paste, or a mixture thereof. The compositions in each
compartment of a multicompartment unit dose article may be
different.
However, typically at least one compartment of the unit dose
article, preferably each compartment, comprises a liquid. The
composition is described in more detail below.
Water-Soluble or Water-Dispersible Film
In some aspects, the detergent composition of the present
disclosure comprises water-soluble or water-dispersible film. The
film may encapsulate the detergent composition, preferably the
first composition. The film may encapsulate a liquid composition, a
granular detergent, a tablet detergent, or mixtures thereof. The
terms water-soluble and water-dispersible are used interchangeably
in the present application.
The film of the present invention is soluble or dispersible in
water. The water-soluble film preferably has a thickness of from
about 20 to about 150 microns, preferably about 35 to about 125
microns, even more preferably about 50 to about 110 microns, most
preferably about 76 microns. Preferably, the film has a
water-solubility of at least 50%, preferably at least 75% or even
at least 95%, as measured by the method set out here after using a
glass-filter with a maximum pore size of 20 microns:
50 grams .+-.0.1 gram of film material is added in a pre-weighed
400 ml beaker and 245 ml.+-.1 ml of distilled water is added. This
is stirred vigorously on a magnetic stirrer, Lab-Line model No.
1250 or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for
30 minutes at 24.degree. C. Then, the mixture is filtered through a
folded qualitative sintered-glass filter with a pore size as
defined above (max. 20 micron). The water is dried off from the
collected filtrate by any conventional method, and the weight of
the remaining material is determined (which is the dissolved or
dispersed fraction). Then, the percentage solubility or
dispersability can be calculated.
Preferred film materials are preferably polymeric materials. The
film material can, for example, be obtained by casting,
blow-molding, extrusion, or blown extrusion of the polymeric
material, as known in the art. Preferably the film is obtained by
an extrusion process or by a casting process.
Preferred polymers (including copolymers, terpolymers, or
derivatives thereof) suitable for use as film material are selected
from polyvinyl alcohols (PVA), polyvinyl pyrrolidone, polyalkylene
oxides, acrylamide, acrylic acid, cellulose, cellulose ethers,
cellulose esters, cellulose amides, polyvinyl acetates,
polycarboxylic acids and salts, polyaminoacids or peptides,
polyamides, polyacrylamide, copolymers of maleic/acrylic acids,
polysaccharides including starch and gelatine, natural gums such as
xanthum and carragum. More-preferred polymers are selected from
polyacrylates and water-soluble acrylate copolymers,
methylcellulose, carboxymethylcellulose sodium, dextrin,
ethylcellulose, hydroxyethyl cellulose, hydroxypropyl
methylcellulose, maltodextrin, polymethacrylates, and most
preferably selected from polyvinyl alcohols, polyvinyl alcohol
copolymers and hydroxypropyl methyl cellulose (HPMC), and
combinations thereof. Preferably, the polymers of the film material
are free of carboxylate groups.
Preferably, the level of polymer in the film material, for example
a PVA polymer, is at least 60%. The polymer can have any weight
average molecular weight, preferably from about 1000 to 1,000,000,
more preferably from about 10,000 to 300,000, yet more preferably
from about 20,000 to 150,000.
Mixtures of polymers can also be used as the film material. This
can be beneficial to control the mechanical and/or dissolution
properties of the compartments or pouch, depending on the
application thereof and the required needs. Suitable mixtures
include for example mixtures wherein one polymer has a higher
water-solubility than another polymer, and/or one polymer has a
higher mechanical strength than another polymer. Also suitable are
mixtures of polymers having different weight average molecular
weights, for example a mixture of PVA or a copolymer thereof of a
weight average molecular weight of about 10,000 to about 40,000,
preferably about 20,000, and of PVA or copolymer thereof, with a
weight average molecular weight of about 100,000 to about 300,000,
preferably about 150,000. Also, suitable herein are polymer blend
compositions, for example comprising hydrolytically degradable and
water-soluble polymer blends such as polylactide and polyvinyl
alcohol, obtained by mixing polylactide and polyvinyl alcohol,
typically comprising about 1-35% by weight polylactide and about
65% to 99% by weight polyvinyl alcohol. Preferred for use herein
are polymers, preferably polyvinyl alcohol, have a degree of
hydrolysis of from about 60% to about 99%, preferably from about
80% to about 99%, even more preferably from about 80% to about 90%,
to improve the dissolution characteristics of the material. As used
herein, the degree of hydrolysis is expressed as a percentage of
vinyl acetate units converted to vinyl alcohol units.
Preferred films exhibit good dissolution in cold water, meaning
unheated distilled water. Preferably such films exhibit good
dissolution at temperatures 24.degree. C., even more preferably at
10.degree. C. By good dissolution it is meant that the film
exhibits water-solubility of at least 50%, preferably at least 75%
or even at least 95%, as measured, by the method set out herein
using a glass-filter with a maximum pore size of 20 microns,
described above. Water-solubility may be determined at 24.degree.
C., or preferably at 10.degree. C.
Preferred films are those supplied by Monosol (Merrillville, Ind.,
USA) under the trade references M8630, M8900, M8779, and M8310
films described in U.S. Pat. Nos. 6,166,117 and 6,787,512, and PVA
films of corresponding solubility and deformability
characteristics. Other suitable films may include called
Solublon.RTM. PT, Solublon.RTM. GA, Solublon.RTM. KC or
Solublon.RTM. KL from the Aicello Chemical Europe GmbH, the films
VF-HP by Kuraray, or the films by Nippon Gohsei, such as Hi Selon.
Further preferred films are those described in US2006/0213801,
US2011/0188784, WO2010/119022, and U.S. Pat. No. 6,787,512. In some
aspects, it is preferable to use a film that exhibits better
dissolution than M8630 film, supplied by Monosol, at temperatures
24.degree. C., even more preferably at 10.degree. C.
Preferred water-soluble films are those derived from a resin that
comprises a blend of polymers, preferably wherein at least one
polymer in the blend is polyvinyl alcohol. Preferably, the
water-soluble film resin comprises a blend of PVA polymers. For
example, the PVA resin can include at least two PVA polymers,
wherein as used herein the first PVA polymer has a viscosity less
than the second PVA polymer. A first PVA polymer can have a
viscosity of at least 8 centipoise (cP), 10 cP, 12 cP, or 13 cP and
at most 40 cP, 20 cP, 15 cP, or 13 cP, for example in a range of
about 8 cP to about 40 cP, or 10 cP to about 20 cP, or about 10 cP
to about 15 cP, or about 12 cP to about 14 cP, or 13 cP.
Furthermore, a second PVA polymer can have a viscosity of at least
about 10 cP, 20 cP, or 22 cP and at most about 40 cP, 30 cP, 25 cP,
or 24 cP, for example in a range of about 10 cP to about 40 cP, or
20 to about 30 cP, or about 20 to about 25 cP, or about 22 to about
24, or about 23 cP. The viscosity of a PVA polymer is determined by
measuring a freshly made solution using a Brookfield LV type
viscometer with UL adapter as described in British Standard EN ISO
15023-2:2006 Annex E Brookfield Test method. It is international
practice to state the viscosity of 4% aqueous polyvinyl alcohol
solutions at 20.degree. C. All viscosities specified herein in cP
should be understood to refer to the viscosity of 4% aqueous
polyvinyl alcohol solution at 20.degree. C., unless specified
otherwise. Similarly, when a resin is described as having (or not
having) a particular viscosity, unless specified otherwise, it is
intended that the specified viscosity is the average viscosity for
the resin, which inherently has a corresponding molecular weight
distribution.
The individual PVA polymers can have any suitable degree of
hydrolysis, as long as the degree of hydrolysis of the PVA resin is
within the ranges described herein. Optionally, the PVA resin can,
in addition or in the alternative, include a first PVA polymer that
has a molecular weight in a range of about 50,000 to about 300,000
Daltons, or about 60,000 to about 150,000 Daltons; and a second PVA
polymer that has a molecular weight in a range of about 60,000 to
about 300,000 Daltons, or about 80,000 to about 250,000
Daltons.
Different film material and/or films of different thickness may be
employed in making the compartments of the present invention. A
benefit in selecting different films is that the resulting
compartments may exhibit different solubility or release
characteristics.
In some aspects, hydrophobically modified polymers are employed.
Polymers suitable for use as whole or part of the backbone of
thehydrophobically modified polymer are preferably selected from
the group consisting of polyvinyl alcohol, polyvinyl acetate,
cellulose ethers, polyethylene oxide, starch, polyvinylpyrrolidone,
polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic
anhydride, styrene maleic anhydride, hydroxyethylcellulose,
methylcellulose, polyethylene glycols, carboxymethylcellulose,
polyacrylic acid salts, alginates, acrylamide copolymers, guar gum,
casein, ethylene-maleic anhydride resin series, polyethylenimine,
ethyl hydroxyethylcellulose, ethyl methylcellulose, and
hydroxyethyl methylcellulose. Copolymer mixtures of polymers
derived from the aforementioned backbones are also suitable.
Preferably the polymer has a backbone comprising side chain
hydroxyl groups, more preferably side chain hydroxyl groups that
are located on carbon atoms spaced 1,2 or 1,3 from one another.
In one aspect, a preferred backbone for hydrophobic modification
comprises polyvinyl alcohol, and the polymer preferably has an
average molecular weight of from 1,000 to 300,000 Daltons,
preferably 2,000 to 100,000 Daltons. Such polyvinyl alcohol
generally comprises at least some polyvinyl acetate (PVAc). The
PVOH materials either before or after hydrophobic modification may
comprise from 0.01 to 40%, preferably from 0.01 to 29%, more
preferably 0.1 to 15%, most preferably 0.5 to 10%, based on the
percent of the total number of monomers making up the polymer. As
used herein, the term polyvinyl alcohol (PvOH) includes PVOH
compounds with PVAc levels as defined hereinabove.
The polymer is modified to comprise hydrophobic substituents.
Preferred derivatization groups include this based on parent groups
selected from acetals, ketals, esters, fluorinated organic
compounds, ethers, alkanes, alkenes, and aromatics. Highly
preferred hydrophobic substituents are hydrocarbyl groups of
C.sub.4 to C.sub.22 carbon chain length, wherein the hydrocarbyl
groups may be alkyl or alkenyl, and may be straight chain or
branched, may comprise rings, may optionally incorporate aromatic
moieties, and combinations thereof. Additional modifying groups,
such as amines, may be present on the polymer backbone.
More preferably the hydrocarbyl group has a chain length from
C.sub.4 to C.sub.20, even more preferably from C.sub.4 to C.sub.15,
most preferably from C.sub.4 to C.sub.10, for example, from C.sub.4
to C.sub.8. Preferred materials suitable for use to introduce the
hydrophobic derivatization groups onto the polymer are aldehydes
such as butyraldehyde, octyl aldehyde, dodecyl aldehyde,
2-ethylhexanal, cyclohexane carboxaldehyde, citral, and
4-aminobutyraldehyde dimethyl acetal. In one aspect, butyraldehyde
is most preferred. Methods of making such hydrophobically modified
polymers are disclosed in the public domain and are readily
available to those skilled in the art.
The hydrophobic material is preferably present in the
hydrophobically modified polymer at a level of 01 to 40% by weight,
based on the total weight of the polymer, more preferably from 2 to
30%, most preferably from 5 to 15%.
In one aspect, the films may be in the form of polymer particles
preferably having a size of greater than or equal to 50
.quadrature.m. Preferably the particle size is from 50
.quadrature.m to 2 cm, preferably from 50 .quadrature.m to 1 cm.
Alternatively the polymer particle may have a size from 0.1 mm to
50 mm; or from 0.5 mm to 10 mm or from 1 to 10 mm, for example. The
size of the particle means the maximum value of the largest
dimension of the particle.
When hydrophobically modified polymer particles are employed, the
size may be either at the low end of the range hereinbefore
defined, such that the particles are less visible, or they may be
of a size near the high end of the range hereinbefore defined if
the particles are intended to be seen.
With respect to hydrophobically modified polyvinyl alcohol films,
the term "insoluble" as used herein means the polymer should not
dissolve in solutions having greater than 5,000 ppm surfactant.
Specifically, when 1 g/L of the modified polymer is placed into an
aqueous surfactant solution comprising a 50:50 weight % mixture of
a linear alkylbenzene sulfonate (LAS) and nonionic surfactant (the
reaction product of aliphatic C.sub.12-C.sub.15 linear alcohols
with 7 mole equivalents of ethylene oxide (7EO)) at a total
surfactant concentration of greater than 5 g/L and shaken at 100
RPM on a rotator shaker at 293K for 2 hours, then removed from
solution by filtering through a sieve or filter paper of
appropriate size and dried, then the weight of modified polymer
removed is within 95% of the weight that was originally added.
Preferably the modified polymer is insoluble in said aqueous
surfactant mixture where the surfactant concentration is from 5 to
800 g/L, more preferably from 5 to 500 g/L, for example from 50 to
500 g/L.
The film material herein, whether hydrophobically modified or not,
can also comprise one or more additive ingredients. For example,
the film preferably comprises a plasticizing agent. The
plasticizing agent may comprise water, glycerol, ethylene glycol,
diethylene glycol, propylene glycol, sorbitol, or mixtures thereof.
In some aspects, the film comprises from about 2% to about 35%, or
from about 5% to about 25%, by weight of the film, a plasticizing
agent selected from group comprising water, glycerol, diethylene
glycol, sorbitol, and mixtures thereof. In some aspects, the film
material comprises at least two, or preferably at least three,
plasticizing agents. In some aspects, the film is substantially
free of ethanol, meaning that the film comprises from 0% (including
0%) to about 0.1% ethanol by weight of the film. In some aspects,
the plasticizing agents are the same as the plasticizing solvents
in the liquid composition, described below.
Other additives may include water and functional detergent
additives, including surfactant, to be delivered to the wash water,
for example, organic polymeric dispersants, etc.
Leuco Colorant
The detergent composition comprises a leuco colorant. Preferably,
at least about 10%, 30%, 50%, 70%, 90%, or even about 95% of the
leuco colorant is incorporated into the water-soluble film. In one
preferred embodiment, substantially all of the leuco colorant is
incorporated into water-soluble film. It will be understood that
the leuco colorant can be incorporated into any part of the
film(s), as discussed above. For example, in one embodiment, the
leuco colorant is incorporated into one of or both of the first
film and/or the second film. In yet another embodiment, the leuco
colorant is incorporated into the common wall and, in one
particularly preferred embodiment substantially all of the leuco
colorant is incorporated into the common wall. An antioxidant may
be incorporated into any part or the entirety of the water-soluble
film.
The leuco colorant typically provides a blue or violet shade to
fabric. Leuco colorants can be used either alone or in combination
with either additional leuco colorants or traditional shading dyes
to create a specific shade of hueing and/or to shade different
fabric types. This may be provided for example by mixing a red and
green-blue dye to yield a blue or violet shade. Preferably the
hueing dye is a blue or violet hueing dye, providing a blue or
violet color to a white cloth or fabric. Such a white cloth treated
with the composition will have a hue angle of 210 to 345, or even a
relative hue angle of 240 to 320, or even a relative hue angle of
250 to 300 (e.g., 250 to 290).
In one aspect, the invention relates to a leuco composition
selected from the group consisting of a diarylmethane leuco, a
triarylmethane leuco, an oxazine leuco, a thiazine leuco, a
hydroquinone leuco, an arylaminophenol leuco and mixtures
thereof.
Suitable diarylmethane leuco compounds for use herein include, but
are not limited to, diarylmethylene derivatives capable of forming
a second colored state as described herein. Suitable examples
include, but are not limited to, Michler's methane, a
diarylmethylene substituted with an --OH group (e.g., Michler's
hydrol) and ethers and esters thereof, a diarylmethylene
substituted with a photocleavable moiety, such as a --CN group
(bis(para-N,N-dimethyl)phenyl)acetonitrile), and similar such
compounds.
In one aspect, the invention relates to a composition comprising
one or more leuco compounds conforming to the group selected
from:
##STR00001## and V
(f) mixtures thereof;
wherein the ratio of Formula I-V to its oxidized form is between
98:2 and 75:25, preferably between 98:2 and 85:15, or between 98:2
and 90:10, or even between 98:2 and 95:5.
In the structure of Formula (I), each individual R.sub.o, R.sub.m
and R.sub.p group on each of rings A, B and C is independently
selected from the group consisting of hydrogen, deuterium and
R.sup.5; each R.sup.5 is independently selected from the group
consisting of halogens, nitro, alkyl, substituted alkyl, aryl,
substituted aryl, alkaryl, substituted alkaryl,
--(CH.sub.2).sub.n--O--R.sup.1,
--(CH.sub.2).sub.n--NR.sup.1R.sup.2, --C(O)R.sup.1, --C(O)OR.sup.1,
--C(O)O.sup.-, --C(O)NR.sup.1R.sup.2, --OC(O)R.sup.1,
--OC(O)OR.sup.1, --OC(O)NR.sup.1R.sup.2, --S(O).sub.2R.sup.1,
--S(O).sub.2OR.sup.1, --S(O).sub.2O.sup.-,
--S(O).sub.2NR.sup.1R.sup.2, --NR.sup.1C(O)R.sup.2,
--NR.sup.1C(O)OR.sup.2, --NR.sup.1C(O)SR.sup.2,
--NRC(O)NR.sup.2R.sup.3, --P(O).sub.2R.sup.1,
--P(O)(OR.sup.1).sub.2, --P(O)(OR.sup.1)O.sup.-, and
--P(O)(O.sup.-).sub.2; wherein the index n is an integer from 0 to
4, preferably from 0 to 1, most preferably 0; wherein two R.sub.o
on different A, B and C rings may combine to form a fused ring of
five or more members; when the fused ring is six or more members,
two R.sub.o on different A, B and C rings may combine to form an
organic linker optionally containing one or more heteroatoms; in
one embodiment two R.sub.o on different A, B and C rings combine to
form a heteroatom bridge selected from --O-- and --S-- creating a
six member fused ring; an R.sub.o and R.sub.m on the same ring or
an R.sub.m and R.sub.p on the same ring may combine to form a fused
aliphatic ring or fused aromatic ring either of which may contain
heteroatoms; on at least one of the three rings A, B or C,
preferably at least two, more preferably at least three, most
preferably all four of the R.sub.o and R.sub.m groups are hydrogen,
preferably all four R.sub.o and R.sub.m groups on at least two of
the rings A, B and C are hydrogen; in some embodiments, all R.sub.o
and R.sub.m groups on rings A, B and C are hydrogen; preferably
each R.sub.p is independently selected from hydrogen, --OR.sup.1
and --NR.sup.1R.sup.2; no more than two, preferably no more than
one of R.sub.p is hydrogen, preferably none are hydrogen; more
preferably at least one, preferably two, most preferably all three
R.sub.p are --NR.sup.1R.sup.2; in some embodiments, one or even two
of the Rings A, B and C may be replaced with an independently
selected C.sub.3-C.sub.9 heteroaryl ring comprising one or two
heteroatoms independently selected from O, S and N, optionally
substituted with one or more independently selected R.sup.5 groups;
G is independently selected from the group consisting of hydrogen,
deuterium, C.sub.1-C.sub.16 alkoxide, phenoxide, bisphenoxide,
nitrite, nitrile, alkyl amine, imidazole, arylamine, polyalkylene
oxide, halides, alkylsulfide, aryl sulfide, or phosphine oxide; in
one aspect the fraction [(deuterium)/(deuterium+hydrogen)] for G is
at least 0.20, preferably at least 0.40, even more preferably at
least 0.50 and most preferably at least 0.60 or even at least 0.80;
wherein any two of R.sup.1, R.sup.2 and R.sup.3 attached to the
same heteroatom can combine to form a ring of five or more members
optionally comprising one or more additional heteroatoms selected
from the group consisting of --O--, --NR.sup.15--, and --S--.
In the structure of Formula (II)-(III), e and f are independently
integers from 0 to 4; each R.sup.20 and R.sup.21 is independently
selected from the group consisting of halogens, a nitro group,
alkyl groups, substituted alkyl groups, --NC(O)OR.sup.1,
--NC(O)SR.sup.1, --OR.sup.1, and --NR.sup.1R.sup.2; each R.sup.25
is independently selected from the group consisting of
monosaccharide moiety, disaccharide moiety, oligosaccharide moiety,
and polysaccharide moiety, --C(O)R.sup.1, --C(O)OR.sup.1,
--C(O)NR.sup.1R.sup.2; each R.sup.22 and R.sup.23 is independently
selected from the group consisting of hydrogen, alkyl groups, and
substituted alkyl groups.
In the structure of Formula (IV), wherein R.sup.30 is positioned
ortho or para to the bridging amine moiety and is selected from the
group consisting of --OR.sup.38 and --NR.sup.36R.sup.37, each
R.sup.36 and R.sup.37 is independently selected from the group
consisting of hydrogen, alkyl groups, substituted alkyl groups,
aryl groups, substituted aryl groups, acyl groups, R.sup.4,
--C(O)OR.sup.1, --C(O)R.sup.1, and --C(O)NR.sup.1R.sup.2; R.sup.38
is selected from the group consisting of hydrogen, acyl groups,
--C(O)OR.sup.1, --C(O)R.sup.1, and --C(O)NR.sup.1R.sup.2; g and h
are independently integers from 0 to 4; each R.sup.31 and R.sup.32
is independently selected from the group consisting of alkyl
groups, substituted alkyl groups, aryl groups, substituted aryl
groups, alkaryl, substituted alkaryl,
--(CH.sub.2).sub.n--O--R.sup.1,
--(CH.sub.2).sub.n--NR.sup.1R.sup.2, --C(O)R.sup.1, --C(O)OR.sup.1,
--C(O)O.sup.-, --C(O)NR.sup.1R.sup.2, --OC(O)R.sup.1,
--OC(O)OR.sup.1, --OC(O)NR.sup.1R.sup.2, --S(O).sub.2R.sup.1,
--S(O).sub.2OR.sup.1, --S(O).sub.2O.sup.-,
--S(O).sub.2NR.sup.1R.sup.2, --NR.sup.1C(O)R.sup.2,
--NR.sup.1C(O)OR.sup.2, --NR.sup.1C(O)SR.sup.2,
--NRC(O)NR.sup.2R.sup.3, --P(O).sub.2R.sup.1,
--P(O)(OR.sup.1).sub.2, --P(O)(OR.sup.1)O--, and
--P(O)(O.sup.-).sub.2; wherein the index n is an integer from 0 to
4, preferably from 0 to 1, most preferably 0; --NR.sup.34R.sup.35
is positioned ortho or para to the bridging amine moiety and
R.sup.34 and R.sup.35 are independently selected from the group
consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted
aryl, alkaryl, substituted alkaryl, and R.sup.4; R.sup.33 is
independently selected from the group consisting of hydrogen,
--S(O).sub.2R.sup.1, --C(O)N(H)R.sup.1; --C(O)OR.sup.1; and
--C(O)R.sup.1; when g is 2 to 4, any two adjacent R.sup.31 groups
may combine to form a fused ring of five or more members wherein no
more than two of the atoms in the fused ring may be nitrogen
atoms.
In the structure of Formula (V), wherein X.sup.40 is selected from
the group consisting of an oxygen atom, a sulfur atom, and
NR.sup.45; R.sup.45 is independently selected from the group
consisting of hydrogen, deuterium, alkyl, substituted alkyl, aryl,
substituted aryl, alkaryl, substituted alkaryl, --S(O).sub.2OH,
--S(O).sub.2O.sup.-, --C(O)OR.sup.1, --C(O)R.sup.1, and
--C(O)NR.sup.1R.sup.2; R.sup.40 and R.sup.41 are independently
selected from the group consisting of
--(CH.sub.2).sub.n--O--R.sup.1,
--(CH.sub.2).sub.n--NR.sup.1R.sup.2, wherein the index n is an
integer from 0 to 4, preferably from 0 to 1, most preferably 0; j
and k are independently integers from 0 to 3; R.sup.42 and R.sup.43
are independently selected from the group consisting of alkyl,
substituted alkyl, aryl, substituted aryl, alkaryl, substituted
alkaryl, --S(O).sub.2R.sup.1, --C(O)NR.sup.1R.sup.2,
--NC(O)OR.sup.1, --NC(O)SR.sup.1, --C(O)OR.sup.1, --C(O)R.sup.1,
--(CH.sub.2).sub.n--O--R.sup.1,
--(CH.sub.2).sub.n--NR.sup.1R.sup.2; wherein the index n is an
integer from 0 to 4, preferably from 0 to 1, most preferably 0;
R.sup.44 is --C(O)R.sup.1, --C(O)NR.sup.1R.sup.2, and
--C(O)OR.sup.1.
In the structures of Formula (I)-(V), wherein any charge present in
any of the preceding groups is balanced with a suitable
independently selected internal or external counterion. Suitable
independently selected external counterions may be cationic or
anionic. Examples of suitable cations include but are not limited
to one or more metals preferably selected from Group I and Group
II, the most preferred of these being Na, K, Mg, and Ca, or an
organic cation such as iminium, ammonium, and phosphonium. Examples
of suitable anions include but are not limited to: fluoride,
chloride, bromide, iodide, perchlorate, hydrogen sulfate, sulfate,
aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate,
phosphate, bicarbonate, carbonate, methosulfate, ethosulfate,
cyanate, thiocyanate, tetrachlorozincate, borate,
tetrafluoroborate, acetate, chloroacetate, cyanoacetate,
hydroxyacetate, aminoacetate, methylaminoacetate, di- and
tri-chloroacetate, 2-chloro-propionate, 2-hydroxypropionate,
glycolate, thioglycolate, thioacetate, phenoxyacetate,
trimethylacetate, valerate, palmitate, acrylate, oxalate, malonate,
crotonate, succinate, citrate, methylene-bis-thioglycolate,
ethylene-bis-iminoacetate, nitrilotriacetate, fumarate, maleate,
benzoate, methylbenzoate, chlorobenzoate, dichlorobenzoate,
hydroxybenzoate, aminobenzoate, phthalate, terephthalate,
indolylacetate, chlorobenzenesulfonate, benzenesulfonate,
toluenesulfonate, biphenyl-sulfonate and chlorotoluenesulfonate.
Those of ordinary skill in the art are well aware of different
counterions which can be used in place of those listed above.
In the structures of Formula (I)-(V), R.sup.1, R.sup.2, R.sup.3,
and R.sup.15 are independently selected from the group consisting
of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,
alkaryl, substituted alkaryl, and R.sup.4; wherein R.sup.4 is a
organic group composed of one or more organic monomers with said
monomer molecular weights ranging from 28 to 500, preferably 43 to
350, even more preferably 43 to 250, wherein the organic group may
be substituted with one or more additional leuco colorant moieties
conforming to the structure of Formula I-V. In one aspect, R.sup.4
is selected from the group consisting of alkyleneoxy (polyether),
oxoalkyleneoxy (polyesters), oxoalkyleneamine (polyamides),
epichlorohydrin, quaternized epichlorohydrin, alkyleneamine,
hydroxyalkylene, acyloxyalkylene, carboxyalkylene,
carboalkoxyalkylene, and sugar. In one aspect, R.sup.4 is selected
from EO, PO, BO, and mixtures thereof, more preferably from EO
alone or from EO/PO mixtures. Where any leuco colorant comprises an
R.sup.4 group with three or more contiguous monomers, that leuco
colorant is defined herein as a "polymeric leuco colorant". One
skilled in the art knows that the properties of a compound with
regard to any of a number of characteristic attributes such as
solubility, partitioning, deposition, removal, staining, etc., are
related to the placement, identity and number of such contiguous
monomers incorporated therein. The skilled artisan can therefore
adjust the placement, identity and number of such contiguous
monomers to alter any particular attribute in a more or less
predictable fashion.
In one aspect, preferred leuco colorants are those giving a second
colored state that is resistant to photofading, sometimes referred
to as photo-resistant leuco colorants. In instances where the
detergent composition is exposed to sunlight, such as may occur if
the detergent composition is packaged in a transparent or
translucent container, a second colored state of the leuco colorant
that resists photofading provides a more accurate indication of the
functional age of the product than one that resists photofading
less well. In most instances the selection of a photo-resistant
leuco colorant is not necessary because the detergent composition
is shielded from exposure to sunlight by the packaging, which is
frequently opaque.
Preferred leuco colorants include those conforming to the structure
of Formula VI,
##STR00002##
wherein each R.sup.4 is independently selected from the group
consisting of H, Methyl, Ethyl,
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H, and mixtures
thereof; preferably at least one R.sup.4 group is
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H; wherein each
index a is independently an integer from 1-100, each index b is
independently an integer from 0-50, and wherein the sum of all the
independently selected a integers in all R.sup.4 groups is no more
than 200, preferably no more than 100, and the sum of all the
independently selected b integers in all R.sup.4 groups is no more
than 100, preferably no more than 50. Preferably at least two
R.sup.4 groups are selected from Methyl and Ethyl, most preferably
at least one N in structure VI is substituted with two R.sup.4
groups selected from Methyl and Ethyl, preferably Me.
Highly preferred leuco colorants include those conforming to the
structure of Formula VII,
##STR00003##
wherein each index c is independently 0, 1 or 2, preferably each c
is 1; each R.sup.4 is independently selected from the group
consisting of H, Me, Et,
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H, and mixtures
thereof; preferably each R.sup.4 is
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H wherein each
index a is independently an integer from 1-50, more preferably
1-25, even more preferably 1-20, 1-15, 1-10, 1-5 or even 1-2; each
index b is independently an integer from 0-25, more preferably
0-15, even more preferably 1-5 or even 1-3 and wherein the sum of
all the independently selected a integers in the leuco colorant is
no more than 100, more preferably no more than 80, most preferably
no more than 60, 40, 20, 10 or even no more than 5, and the sum of
all the independently selected b integers in the leuco colorant is
no more than 50, more preferably no more than 40, most preferably
no more than 30, 20, or even 10. In a particularly preferred
aspect, each index c is 1, each R.sup.4 is
((CH.sub.2CH.sub.2O).sub.a(C.sub.3H.sub.6O).sub.b)H, each index a
is an integer from 1-5, each index b is an integer from 1-5, the
sum of all the independently selected a integers in the leuco
compound is from 4 to 10, and the sum of all the independently
selected b integers in the leuco colorant is from 5 to 15.
In another aspect, highly preferred leuco compounds include those
conforming to the structure of Formula (VIII),
##STR00004##
wherein R.sup.8 is H or CH.sub.3 and each index b is independently
on average about 1 to 2.
The leuco triarylmethane compounds described herein can be produced
by any suitable synthetic method. For example, such compounds can
be produced via an acid catalyzed condensation reaction between an
aromatic aldehyde and an electron-rich aryl coupler (e.g., in an
amount of approximately 2 molar equivalents of aryl coupler to 1
molar equivalent of aromatic aldehyde). The aromatic aldehyde can
be any suitable compound comprising an aromatic moiety (e.g., an
aryl moiety, a substituted aryl moiety, a heteroaromatic moiety, or
a substituted heteroaromatic moiety) having an aldehyde group
covalently attached thereto. In one aspect, the aromatic aldehyde
preferably is a substituted benzaldehyde comprising, preferably in
the para position relative to the aldehyde group, a group having
the structure --OR.sup.1 or --NR.sup.1R.sup.2. In another aspect,
the aromatic aldehyde preferably is a substituted benzaldeyde
comprising the group --NR.sup.1R.sup.2 in the para position
relative to the aldehyde group, wherein R.sup.1 and R.sup.2 are
selected from the group consisting of hydrogen, methyl, or ethyl
(more preferably methyl).
As noted above, the condensation reaction utilizes an aryl coupler
in addition to the aromatic aldehyde. To produce the leuco
triarylmethane compound, the condensation reaction generally
utilizes at least two molar equivalents of aryl coupler for each
molar equivalent of aromatic aldehyde. In one aspect, the two molar
equivalents of aryl coupler utilized in the reaction can be
provided using a single aryl coupler compound. In another aspect,
the reaction can be performed using two molar equivalents of a
mixture of two or more distinct aryl couplers. In such an
embodiment, the two or more distinct aryl couplers can be used in
any combination or relative ratios provided the mixture sums to at
least about two molar equivalents of aryl couplers for each molar
equivalent of aromatic aldehyde. In such an embodiment, the two or
more distinct aryl couplers can differ in terms of, for example,
the number and/or nature of the substituents attached to the aryl
moiety. In one aspect, the reaction can utilize a first aryl
coupler comprising a first oxyalkylene or polyoxyalkylene moiety
having a first distribution of oxyalkylene groups and a second aryl
coupler comprising a second oxyalkylene or polyoxyalkylene moiety
having a second distribution of oxyalkylene groups that is
different from the first distribution. For example, in one aspect,
the first aryl coupler can comprise an oxyalkylene moiety
consisting of ethylene oxide groups, such as AC-I below, and the
second aryl coupler can comprise a polyoxyalkylene moiety
consisting of ethylene oxide groups and propylene oxide groups,
such as AC-II below.
##STR00005##
wherein the indices a, b, c and d are independently selected from
integers from 0 to 5; the sum of a and b for a coupler selected
from AC-I and AC-II is from 2 to 10, and the sum of c and d in
AC-II is from 2 to 10. In a more particular aspect, the sum of a
and b for a coupler selected from AC-I and AC-II is from 2 to 5,
and the sum of c and d in AC-II is from 2 to 5. In one embodiment,
the sum of the indices a and b in AC-I is 2 or 3; the sum of the
indices a and b in AC-II is 2 or 3 and the sum of the indices c and
d in AC-II is 1 to 5, preferably 2 to 4 or even 2 to 3. The
couplers AC-I and AC-II may be combined in any proportion provided
the amount of the couplers used is sufficient to provide at least
two molar equivalents relative to the equivalents of the aromatic
aldehyde used in the acid-catalyzed condensation reaction that
gives rise to the leuco compound.
In one aspect, for example, one equivalent of
para-N,N-dimethylbenzaldehyde is condensed with a mixture of at
least two molar equivalents of the aryl couplers AC-I and AC-II
shown above wherein for aryl coupler AC-I, the indices a and b sum
to 2 or 3, preferably 2, and wherein preferably a and b are each 1;
and wherein for aryl coupler AC-II, the indices a and b sum to 2 or
3, preferably 2, and wherein preferably a and b are each 1, and the
indices c and d sum to an average of about 2.5 to 3.0, and wherein
at least one of c or d is 1.
The detergent composition of the present disclosure comprises
water-soluble film which comprises the leuco colorant, meaning that
the leuco colorant may be an integral part of the film and/or in
contact with an exterior surface of the film. The leuco colorant
may be added to the film-forming polymeric material prior to
forming the film, for example prior to extruding or casting the
film. The leuco colorant may be on an exterior surface of the
water-soluble film, where an interior surface is in contact with
the first composition. The leuco colorant may be applied to the
exterior surface of the film by any suitable means. For example,
the leuco colorant may be applied to the exterior of the film by
dusting, powdering, coating, painting, printing, spraying,
atomizing, or mixtures thereof. In some aspects, the leuco colorant
is applied to the unit dose composition by spraying or atomizing a
composition comprising the leuco colorant and a plasticizing
solvent, which is described below. When the leuco colorant is
sprayed or atomized onto a film, the sprayed or atomized
composition may be non-aqueous, meaning that it comprises less than
20%, or less than 15%, or less than 10%, or less than 5%, or less
than 1% water by weight of the sprayed or atomized composition. The
sprayed or atomized composition may even comprise zero percent
water.
The detergent composition may comprise a coating, where the coating
comprises the leuco colorant.
In some aspects, the concentration of the leuco colorant on the
surface of the film is from about 10 ppb to about 10,000 ppm, or
preferably from about 50 ppb to about 200 ppm, or more preferably
from about 10 ppm to about 250 ppm. In some aspects, the
concentration of the leuco colorant is determined after storage of
the unit dose article for one month at 25.degree. C. and 60%
relative humidity.
In one preferred embodiment, the leuco colorant is encapsulated
separately or isolated from other components in the water-soluble
film, for example, via capsules or microcapsules. It will be
understood that when present in a capsules or microcapsule, the
leuco colorants second color state can be blocked or otherwise
distorted.
Detergent Adjuncts
The detergent composition may comprise other suitable adjuncts
which, in some aspects, can be wholly or partially incorporated
into the film. Adjuncts may be selected according to the detergent
composition's intended function. The first composition may comprise
an adjunct. In some aspects, in the case of multi-compartment unit
dose articles, the adjuncts may be part of a non-first (e.g.,
second, third, fourth, etc.) composition encapsulated in
compartments separate from the first composition. The non-first
composition may be any suitable composition. The non-first
composition may be in the form of a solid, a liquid, a dispersion,
a gel, a paste or a mixture thereof. Where the unit dose comprises
multiple compartments, the leuco colorant may be added to or
present in one, two, or even all the compartments.
Non-limiting examples of detergent compositions include cleaning
compositions, fabric care compositions and hard surface cleaners.
More particularly, the compositions may be a laundry, fabric care
or dish washing composition including, pre-treatment or soaking
compositions and other rinse additive compositions. The composition
may be a fabric detergent composition or an automatic dish washing
composition. The fabric detergent composition may be used during
the main wash process or could be used as pre-treatment or soaking
compositions.
Fabric care compositions include fabric detergents, fabric
softeners, 2-in-1 detergent and softening, pre-treatment
compositions and the like. Fabric care compositions may comprise
typical fabric care adjuncts, including surfactants, builders,
chelating agents, dye transfer inhibiting agents, dispersants,
enzymes, and enzyme stabilizers, plasticizing solvents, catalytic
materials, bleach activators, polymeric dispersing agents, clay
soil removal/anti-redeposition agents, brighteners, suds
suppressors, dyes, additional perfume and perfume delivery systems,
structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids and/or pigments and mixtures thereof.
The composition may be a laundry detergent composition comprising
an adjunct selected from the group comprising a surfactant,
polymers, perfumes, encapsulated perfume materials, structurant and
mixtures thereof.
The composition may be an automatic dish washing composition
comprising an adjunct selected from surfactant, builder,
sulfonated/carboxylated polymer, silicone suds suppressor,
silicate, metal and/or glass care agent, enzyme, bleach, bleach
activator, bleach catalyst, source of alkalinity, perfume, dye,
solvent, filler and mixtures thereof.
Preferably, the liquid composition comprises a surfactant.
Surfactants can be selected from anionic, cationic, zwitterionic,
non-ionic, amphoteric or mixtures thereof. Preferably, the unit
dose composition comprises anionic surfactant, non-ionic
surfactant, or mixtures thereof. The detergent composition,
preferably the liquid composition, may comprise from about 1% to
about 70%, or from about 3% to about 50%, or from about 5% to about
25%, by weight of a surfactant system.
The anionic surfactant may be selected from linear alkyl benzene
sulfonate, alkyl ethoxylate sulphate and combinations thereof.
Suitable anionic surfactants useful herein can comprise any of the
conventional anionic surfactant types typically used in liquid
detergent products. These include the alkyl benzene sulfonic acids
and their salts as well as alkoxylated or non-alkoxylated alkyl
sulfate materials.
Suitable nonionic surfactants for use herein include the alcohol
alkoxylate nonionic surfactants. Alcohol alkoxylates are materials
which correspond to the general formula:
R.sup.1(C.sub.mH.sub.2mO).sub.nOH wherein R.sup.1 is a
C.sub.8-C.sub.16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12. In one aspect, R.sup.1 is an alkyl group, which may
be primary or secondary, that comprises from about 9 to 15 carbon
atoms, or from about 10 to 14 carbon atoms. In one aspect, the
alkoxylated fatty alcohols will also be ethoxylated materials that
contain from about 2 to 12 ethylene oxide moieties per molecule, or
from about 3 to 10 ethylene oxide moieties per molecule.
The compositions can comprise one or more detergent enzymes which
provide cleaning performance and/or fabric care benefits. Examples
of suitable enzymes include, but are not limited to,
hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases, phospholipases, esterases, cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,
-glucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, and amylases, or mixtures thereof. A typical combination
is a cocktail of conventional applicable enzymes like protease,
lipase, cutinase and/or cellulase in conjunction with amylase.
The compositions of the present invention may comprise one or more
bleaching agents. Suitable bleaching agents other than bleaching
catalysts include photobleaches, bleach activators, hydrogen
peroxide, sources of hydrogen peroxide, pre-formed peracids and
mixtures thereof. In general, when a bleaching agent is used, the
compositions of the present invention may comprise from about 0.1%
to about 50% or even from about 0.1% to about 25% bleaching agent
by weight of the cleaning composition.
The composition may comprise a brightener. Suitable brighteners are
stilbenes, such as brightener 15. Other suitable brighteners are
hydrophobic brighteners, and brightener 49. The brightener may be
in micronized particulate form, having a weight average particle
size in the range of from 3 to 30 micrometers, or from 3
micrometers to 20 micrometers, or from 3 to 10 micrometers. The
brightener can be alpha or beta crystalline form.
The compositions herein may also optionally contain one or more
copper, iron and/or manganese chelating agents. If utilized,
chelating agents will generally comprise from about 0.1% by weight
of the compositions herein to about 15%, or even from about 3.0% to
about 15% by weight of the compositions herein. Suitable chelants
include a chelant selected from the group consisting of DTPA
(Diethylene triamine pentaacetic acid), HEDP (Hydroxyethane
diphosphonic acid), DTPMP (Diethylene triamine penta(methylene
phosphonic acid)), ethylenediaminedisuccinic acid (EDDS),
1,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt hydrate, and
derivatives of such chelants.
The composition may comprise a calcium carbonate crystal growth
inhibitor, such as one selected from the group consisting of:
1-hydroxyethanediphosphonic acid (HEDP) and salts thereof;
N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts
thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid and salts
thereof; and any combination thereof. The compositions of the
present disclosure may also include one or more dye transfer
inhibiting agents. Suitable polymeric dye transfer inhibiting
agents include, but are not limited to, polyvinylpyrrolidone
polymers, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and
polyvinylimidazoles or mixtures thereof. When present in the
compositions herein, the dye transfer inhibiting agents are present
at levels from about 0.0001%, from about 0.01%, from about 0.05% by
weight of the cleaning compositions to about 10%, about 2%, or even
about 1% by weight of the cleaning compositions.
The composition may comprise one or more polymers. Suitable
polymers include carboxylate polymers, polyethylene glycol
polymers, polyester soil release polymers such as terephthalate
polymers, amine polymers, cellulosic polymers, dye transfer
inhibition polymers, dye lock polymers such as a condensation
oligomer produced by condensation of imidazole and epichlorhydrin,
optionally in ratio of 1:4:1, hexamethylenediamine derivative
polymers, and any combination thereof.
Other suitable cellulosic polymers may have a degree of
substitution (DS) of from 0.01 to 0.99 and a degree of blockiness
(DB) such that either DS+DB is of at least 1.00 or DB+2DS-DS.sup.2
is at least 1.20. The substituted cellulosic polymer can have a
degree of substitution (DS) of at least 0.55. The substituted
cellulosic polymer can have a degree of blockiness (DB) of at least
0.35. The substituted cellulosic polymer can have a DS+DB, of from
1.05 to 2.00. A suitable substituted cellulosic polymer is
carboxymethylcellulose.
Another suitable cellulosic polymer is cationically modified
hydroxyethyl cellulose.
Suitable perfumes include perfume microcapsules, polymer assisted
perfume delivery systems including Schiff base perfume/polymer
complexes, starch-encapsulated perfume accords, perfume-loaded
zeolites, blooming perfume accords, and any combination thereof. A
suitable perfume microcapsule is melamine formaldehyde based,
typically comprising perfume that is encapsulated by a shell
comprising melamine formaldehyde. It may be highly suitable for
such perfume microcapsules to comprise cationic and/or cationic
precursor material in the shell, such as polyvinyl formamide (PVF)
and/or cationically modified hydroxyethyl cellulose (catHEC).
Suitable suds suppressors include silicone and/or fatty acid such
as stearic acid.
When the detergent composition comprises a liquid composition
encapsulated by the water-soluble film, the liquid composition
preferably comprises a plasticizing solvent. The liquid composition
may comprise from about 10% to about 50%, or from about 15% to
about 40%, by weight of the liquid composition, of the plasticizing
solvent.
The plasticizing solvent in the present compositions can be a
plasticizing solvent containing water, organic solvent, or mixtures
thereof. Suitable organic solvents include low molecular weight
alcohols and/or low molecular weight glycols, wherein "low
molecular weight" in this context means having a molecular weight
of less than about 500. Suitable organic solvents preferably
include glycerol, 1,2-propanediol, 1,3-propanediol, dipropylene
glycol, diethylene glycol, sorbitol, and mixtures thereof. In some
aspects, the plasticizing solvent comprises water, glycerol,
1,2-propanediol, 1-3-propanediol, dipropylene glycol, diethylene
glycol, sorbitol, or mixtures thereof.
Anti-Oxidant
The composition may optionally contain an anti-oxidant present from
about 0.001 to about 2% by weight. Preferably the antioxidant is
present at a concentration in the range 0.01 to 0.1% by weight.
Mixtures of anti-oxidants may be used and in some embodiments, may
be preferred. One or more antioxidants may be incorporated into any
part or the entirety of the water-soluble film. In a preferred
embodiment, an antioxidant is incorporated into the water-soluble
film along with the leuco colorant.
Anti-oxidants are substances as described in Kirk-Othmer (Vol. 3,
page 424) and in Ullmann's Encyclopedia (Vol. 3, page 91).
One class of anti-oxidants used in the present invention is
alkylated phenols, having the general formula:
##STR00006##
wherein R is C.sub.1-C.sub.22 linear or branched alkyl, preferably
methyl or branched C.sub.3-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy,
preferably methoxy, or CH.sub.2CH.sub.2C(O)OR', wherein R' is H, a
charge balancing counterion or C.sub.1-C.sub.22 linear or branched
alkyl; R.sub.1 is a C.sub.3-C.sub.6 branched alkyl, preferably
tert-butyl; x is 1 or 2. Hindered phenolic compounds are a
preferred type of alkylated phenols having this formula. A
preferred hindered phenolic compound of this type is
3,5-di-tert-butyl-4-hydroxytoluene (BHT).
Furthermore, the anti-oxidant used in the composition may be
selected from the group consisting of .alpha.-, .beta.-, .gamma.-,
.delta.-tocopherol, ethoxyquin,
2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl
hydroquinone, tert-butyl hydroxyanisole, lignosulphonic acid and
salts thereof, and mixtures thereof. It is noted that ethoxyquin
(1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is marketed under
the name Raluquin.TM. by the company Raschig.TM..
Other types of anti-oxidants that may be used in the composition
are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid
(Trolox.TM.) and 1,2-benzisothiazoline-3-one (Proxel GXL.TM.).
A further class of anti-oxidants which may be suitable for use in
the composition is a benzofuran or benzopyran derivative having the
formula:
##STR00007##
wherein R.sub.1 and R.sub.2 are each independently alkyl or R.sub.1
and R.sub.2 can be taken together to form a C.sub.5-C.sub.6 cyclic
hydrocarbyl moiety; B is absent or CH.sub.2; R.sub.4 is
C.sub.1-C.sub.6 alkyl; R.sub.5 is hydrogen or --C(O)R.sub.3 wherein
R.sub.3 is hydrogen or C.sub.1-C.sub.19 alkyl; R.sub.6 is
C.sub.1-C.sub.6 alkyl; R.sub.7 is hydrogen or C.sub.1-C.sub.6
alkyl; X is --CH.sub.2OH, or --CH.sub.2A wherein A is a nitrogen
comprising unit, phenyl, or substituted phenyl. Preferred nitrogen
comprising A units include amino, pyrrolidino, piperidino,
morpholino, piperazino, and mixtures thereof.
Anti-oxidants such as tocopherol sorbate, butylated hydroxyl
benxoic acids and their salts, gallic acid and its alkyl esters,
uric acid and its salts, sorbic acid and its salts, and
dihydroxyfumaric acid and its salts may also be used. In one
aspect, the most preferred types of anti-oxidant for use in the
composition are 3,5-di-tert-butyl-4-hydroxytoluene (BHT), .alpha.-,
.beta.-, .gamma.-, .delta.-tocopherol, 1,2-benzisothiazoline-3-one
(Proxel GXL.TM.) and mixtures thereof. In another aspect, the most
preferred types of anti-oxidant for use in the composition are
hindered phenols, diarylamines (including phenoxazines with a
maximum molar extinction coefficient in the wavelength range from
400 to 750 nm of less than 1,000 M.sup.-1 cm.sup.-1), and mixtures
thereof. In preferred mixtures, the number of equivalents of
hindered phenol initially formulated will normally be greater than
or equal to the number of equivalents of diarylamine.
Process for Washing
The present disclosure also relates to a process for the washing,
for example by machine, of laundry or dishware using a composition
according to the present disclosure, comprising the steps of,
placing a detergent composition according to the present disclosure
into contact with the laundry or dishware to be washed, and
carrying out a washing or cleaning operation.
Any suitable washing machine may be used. Those skilled in the art
will recognize suitable machines for the relevant wash operation.
The article of the present invention may be used in combination
with other compositions, such as fabric additives, fabric
softeners, rinse aids, and the like.
Additionally, the detergent compositions of the present disclosure
may be used in known hand washing methods.
Process for Making
The present disclosure relates to a method of making a detergent
composition. More specifically, the present disclosure relates to a
method of making a detergent composition comprising a first
composition, a water-soluble film and a leuco colorant, where the
method comprises the step of incorporating the leuco colorant into
the water-soluble film. The incorporating step may be according to
any suitable method of making a detergent composition known to one
of ordinary skill, for example by spraying, atomizing, or mixtures
thereof said leuco colorant into said film. In such embodiments,
the leuco colorant may be added to the film composition prior to
casting or extrusion of the film
Where the first composition is a granular detergent or a tablet
detergent, the method comprises the step of encasing the first
composition in either a water-soluble film or a water-soluble
coating. Alternatively, the method may comprise the step of
providing the first composition already encased in either a
water-soluble film or a water-soluble coating.
In some aspects, the present disclosure relates to making a film
comprising a leuco colorant, wherein the method comprises the steps
of providing a liquid composition comprising a leuco colorant and a
plasticizing solvent, and contacting a water-soluble film with the
liquid composition, wherein the film comprises a plasticizing
agent. The film may be formed into a pouch and sealed, thereby
forming a sealed pouch. In some aspects, the sealed pouch
encapsulates surfactant. In some aspects, the contacting results
from filling the pouch with the liquid composition. In some
aspects, the contacting results from spraying or atomizing said
liquid composition onto said film. The film may be formed into a
pouch after the spraying or atomizing.
The method of making unit dose articles is described in more detail
below.
The process of the present disclosure may be continuous or
intermittent. The process comprises the general steps of forming an
open pouch, preferably by forming a water-soluble film, which may
comprise a leuco colorant, into a mould to form said open pouch,
filling the open pouch with a composition, closing the open pouch
filled with a composition, preferably using a second water-soluble
film, which may comprise a leuco colorant, to form the unit dose
article. The second film may also comprise additional compartments,
which may or may not comprise compositions. Alternatively, the
second film may be a second closed pouch containing one or more
compartments, used to close the open pouch. Preferably, the process
is one in which a web of unit dose article are made, said web is
then cut to form individual unit dose articles.
Alternatively, the first film may be formed into an open pouch
comprising more than one compartment. In which case, the
compartments formed from the first pouch may be in a side-by-side
or `tire and rim` orientation. The second film may also comprise
compartments, which may or may not comprise compositions.
Alternatively, the second film may be a second closed pouch used to
close the multicompartment open pouch.
The unit dose article may be made by thermoforming, vacuum-forming
or a combination thereof. Unit dose articles may be sealed using
any sealing method known in the art. Suitable sealing methods may
include heat sealing, solvent sealing, pressure sealing, ultrasonic
sealing, pressure sealing, laser sealing or a combination thereof.
Examples of continuous in-line processes of manufacturing
water-soluble containers are set forth in U.S. Pat. No. 7,125,828,
U.S. 2009/0199877A1, EP 2380965, EP 2380966, U.S. Pat. No.
7,127,874 and US2007/0241022 (all to Procter & Gamble Company,
Ohio, USA). Examples of non-continuous in-line processes of
manufacturing water-soluble containers are set forth in U.S. Pat.
No. 7,797,912 (to Reckitt Benckiser, Berkshire, GB).
The unit dose articles may be dusted with a dusting agent. Dusting
agents can include talc, silica, zeolite, carbonate or mixtures
thereof.
An exemplary means of making the unit dose article of the present
disclosure is a continuous process for making an article,
comprising the steps of:
a. continuously feeding a first water-soluble film, which may
comprise a leuco colorant, onto a horizontal portion of an
continuously and rotatably moving endless surface, which comprises
a plurality of moulds, or onto a non-horizontal portion thereof and
continuously moving the film to said horizontal portion; b. forming
from the film on the horizontal portion of the continuously moving
surface, and in the moulds on the surface, a continuously moving,
horizontally positioned web of open pouches; c. filling the
continuously moving, horizontally positioned web of open pouches
with a product, to obtain a horizontally positioned web of open,
filled pouches; d. preferably continuously, closing the web of open
pouches, to obtain closed pouches, preferably by feeding a second
water-soluble film, which may comprise a leuco colorant, onto the
horizontally positioned web of open, filed pouches, to obtain
closed pouches; and e. optionally sealing the closed pouches to
obtain a web of closed pouches.
The second water-soluble film may comprise at least one open or
closed compartment.
In one embodiment, a first web of open pouches is combined with a
second web of closed pouches preferably wherein the first and
second webs are brought together and sealed together via a suitable
means, and preferably wherein the second web is a rotating drum
set-up. In such a set-up, pouches are filled at the top of the drum
and preferably sealed afterwards with a layer of film, the closed
pouches come down to meet the first web of pouches, preferably open
pouches, formed preferably on a horizontal forming surface. It has
been found especially suitable to place the rotating drum unit
above the horizontal forming surface unit.
Preferably, the resultant web of closed pouches is cut to produce
individual unit dose articles.
EXAMPLES
Formulation Examples
All levels are in weight percent of the composition.
Example 1--Mono Compartment Pouches
Mono compartment pouches are filled with liquid detergents of
composition 1.1, shown in Table 1. The pouches are made using a
water-soluble poly(vinyl alcohol film comprising a leuco colorant
(e.g., Leuco colorant 1) and optionally, an antioxidant (e.g.,
3,5-di-tert-butyl-4-hydroxytoluene), and formed using standard
thermoforming techniques. Specifically, 0.7 g of a 76 .mu.m thick
film M8779 and 0.0025 g of Dye Formula 8, shown above, are
thermoformed to form a single compartment pouch measuring 41 mm by
43 mm. The pouch is filled with 23.7 mL (25.4 g) of composition
1.1.
TABLE-US-00001 TABLE 1 Ingredients Composition 1.1 Linear
C.sub.9-C.sub.15 Alkylbenzene sulfonic acid 20 C.sub.12-14 alkyl
9-ethoxylate 15 Citric Acid 1 Fatty acid 8 C12-14 alkyl ethoxy 3
sulfate 9 Chelant 1 Polymer 7 Enzymes 1 Structurant 0.15 Glycerol 6
1,2 propanediol 11 Water 10 Mono-ethanolamine or NaOH (or mixture
neutralize to pH to thereof) about 7.4 Additives, Minor To 100%
Example 2--Multi Compartment Pouches
Examples of multicompartment pouches can include the formulations
presented in Table 2. The pouches are made with water-soluble film,
at least a portion of which is as the film described in Example 1
above.
TABLE-US-00002 TABLE 2 2.1 2.2 2.3 3 compartments 2 compartments 3
compartments Compartment # 1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5
30.0 5.0 25.0 1.5 4.0 Ingredients Weight % Alkylbenzene sulfonic
acid 20.0 20.0 20.0 10.0 20.0 20.0 Alkyl sulfate 2.0 C12-14 alkyl
7-ethoxylate 17.0 17.0 17.0 17.0 17.0 Cationic surfactant 1.0
Zeolite A 10.0 C12-18 Fatty acid 13.0 13.0 13.0 18.0 18.0 Sodium
acetate 4.0 Enzymes 0-3 0-3 0-3 0-3 0-3 Sodium Percarbonate 11.0
TAED 4.0 Organic catalyst .sup.1 1.0 PAP granule .sup.2 50
Polycarboxylate 1.0 Ethoxysulfated 2.2 2.2 2.2 Hexamethylene
Diamine Dimethyl Quat Hydroxyethane 0.6 0.6 0.6 0.5 diphosphonic
acid Ethylene diamine 0.4 tetra(methylene phosphonic) acid
Brightener 0.2 0.2 0.2 0.3 0.3 Alkoxylated polyamine.sup.6 5 4 7
Leuco colorant.sup.4 0.05 0.035 0.12 Perfume 1.7 1.7 0.6 1.5 Water
10.0 10.0 10.0 4.0 Glycerol 5 6 10 Sorbitol 1 Propane diol 5 5 5 30
11 89 Buffers (sodium To pH 8.0 for liquids carbonate, To RA
>5.0 for powders monoethanolamine) .sup.5 Minors (antioxidant,
To 100% aesthetics, . . .), sodium sulfate for powders .sup.1
Sulfuric acid
mono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]
ester as described in U.S. Pat. No. 7,169,744 .sup.2 PAP =
Phthaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake .sup.3
Polyethylenimine (molecular weight = 600) with 20 ethoxylate groups
per --NH. .sup.4Leuco colorant 1, shown below; At least 10%,
preferably at least 50% of the leuco colorant present is
incorporated in at least one of the multiple films that comprise
the article. .sup.5 RA = Reserve Alkalinity (g NaOH/dose)
.sup.6PEI600 EO20, available from BASF
Example 3--Incorporation of a Leuco Colorant into a Film and
Changes in Color Upon Aging
In order to demonstrate the usefulness of leuco colorants
incorporated into a film, three different poly(vinyl alcohol) films
were prepared. A 15.51 wt % solution of PVOH in DI water (control,
Solution C) was prepared by mixing 110.0 g DI water and 20.2 g PvOH
in a glass jar, placing the cap on the jar and heating at
40.degree. C. for two days. Separately, 0.143 g of Leuco Colorant 1
was dissolved in 5.0 mL ethanol, and this was mixed until
homogeneous with 117.0 g Solution C to obtain Solution L The
structure of the leuco colorant tested is shown below.
##STR00008##
Finally, 0.0422 g of 3,5-di-tert-butyl-4-hydroxy toluene (BHT) was
dissolved in 5.0 mL ethanol and this was mixed with 50.0 g Solution
L to obtain Solution LA. The final composition of the solutions is
provided in the table below.
TABLE-US-00003 Ingredient Weight % Ingredient Solution C Solution L
Solution LA PVOH 15.51 14.87 14.10 Leuco Colorant 1.sup.a -- 0.117
0.106 BHT -- -- 0.0767
For each of the three solutions, 12 films were cast by transferring
via disposable syringe 4.0 mL of the solution into each of the
wells on two six-well plates. The plates were placed uncovered into
an oven set at 30.degree. C. and allowed to stand undisturbed for
65.5 hours. A single piece of film cast from each solution was
removed and the L*, a*, b* and WI CIE were measured using a LabScan
XE reflectance spectrophotometer (HunterLabs, Reston, Va.; D65
illumination, 10.degree. observer, UV light excluded).
The films were then stored in the dark at room temperature and
periodically the film cast from each Solution was removed and
measured again to record any changes. As the Leuco Colorant
converts from the first colored state to the second colored state,
blue color becomes visible. This is observed in the measurements as
a change in the b* value, where a lower b* indicates more blue
color formation. The b* values measured for the films on various
days are gathered in the table below.
TABLE-US-00004 Time (days) Film cast from Solution 3 12 24 49 327 C
2.18 2.18 1.62 1.76 2.92 L -7.48 -12.99 -21.23 -29.99 -59.32 LA
0.20 -1.03 -2.99 -6.32 -18.78
The above data shows that the incorporation of Leuco Colorant into
film leads to a shift in color of the film over time, and that the
extent of the color that develops can be changed by the
incorporation of an antioxidant into the film. Thus, use of a leuco
colorant in a film is an effective way to communicate visually that
a product employing the film has aged to a certain extent. If the
leuco colorant employed deposits on fabric through the wash, as is
known to be the case for the colorant employed in this example, use
of the film serves a dual purpose, indicating the age of the
product and providing a whiteness benefit to fabrics.
The dimensions and values disclosed herein are not to be understood
as being strictly limited to the exact numerical values recited.
Instead, unless otherwise specified, each such dimension is
intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm."
Every document cited herein, including any cross referenced or
related patent or application and any patent application or patent
to which this application claims priority or benefit thereof, is
hereby incorporated herein by reference in its entirety unless
expressly excluded or otherwise limited. The citation of any
document is not an admission that it is prior art with respect to
any invention disclosed or claimed herein or that it alone, or in
any combination with any other reference or references, teaches,
suggests or discloses any such invention. Further, to the extent
that any meaning or definition of a term in this document conflicts
with any meaning or definition of the same term in a document
incorporated by reference, the meaning or definition assigned to
that term in this document shall govern.
While particular embodiments of the present invention have been
illustrated and described, it would be obvious to those skilled in
the art that various other changes and modifications can be made
without departing from the spirit and scope of the invention. It is
therefore intended to cover in the appended claims all such changes
and modifications that are within the scope of this invention.
* * * * *